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Active, heterogeneous bi- or tri-dentate catalyst

a bior tridentate catalyst, heterogeneous technology, applied in catalyst activation/preparation, chemical/physical processes, group 3/13 element organic compounds, etc., can solve the problems of metallocene sensitivity, high catalyst cost, and difficult handling of activaters, and achieve high catalytic activity

Inactive Publication Date: 2007-11-06
SHIH KENG YU
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0017]The present invention partly relies on the discovery that activation of a bidentate and / or tridentate ligand / transition metal complex is very sensitive to the level of aluminum compound used according to the present invention and that said activation is induced by extremely low amounts of said compound. This has the benefit of further reducing the cost of the catalyst system and eliminates the need for expensive and difficult to handle aluminoxanes or borate activators of the prior art. In addition, the present invention partly relies on the discovery that immobilization of the transition metal complex occurs by the present process without any special impregnation step and the slurry of the present invention having the activated catalyst can be used directly or formed in situ in an olefin polymerization process.

Problems solved by technology

Such activators are expensive and difficult to handle due to their pyrophoric properties and unstable character.
Further, catalyst systems formed with these activators are difficult to effectively anchor or immobilized onto a support and, therefore, the catalyst tend to resolubilize from or leach out of the support causing fouling within the polymerization reactor.
The required use of aluminoxane in large quantities to provide a catalyst of suitable activity, the need to initially form the aluminoxane followed by its combining with certain catalysts compounds in a multi-step process, the sensitivity of metallocenes to commonly encountered impurities and the poor morphology of resultant polymer product are all known disadvantages of such catalyst systems.
However, the presence of large amounts of aluminoxane in such systems cause chain transfer reaction to occur and thereby predominantly produce low molecular weight oligomer products.
For example, coordination catalysts are known to be extremely sensitive to moisture and air and their activity is greatly reduced or destroyed by such elements.

Method used

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  • Active, heterogeneous bi- or tri-dentate catalyst
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  • Active, heterogeneous bi- or tri-dentate catalyst

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0098]The following Table 1 below displays the catalyst composition (AliBu3 and Fe tridentate compound loadings) and performance (i.e. catalyst activity, Fe metal efficiency, and bulk density of the resulting polymer particles). The catalysts listed in Table 1 below were prepared by adding Grace Davison 955 silica (10 μm, 300 m2 / g, 1.6 cc / g, 3.5% TV @ 1750° F.), AliBu3 solution (1 M in toluene), and a tridentate ligand / transition metal complex, 2,6-bis(2,4,6-trimethylarylimino)pyridyl iron dichloride. These components were added sequentially into a 25 ml toluene solution under argon atmosphere in the manner described in Section A above. The AliBu3 and Fe compound loadings were based on per gram of silica in the 25-ml toluene solution. A portion of this catalyst slurry was then used for polymerization testing according to the polymerization method described in Section B above. The polymerization conditions were at 70° C., 200 psig and the H2 / ethylene ratio was ˜0.05.

[0099]

TABLE 1AliB...

example 2

[0101]The same catalyst preparation and polymerization conditions as in Example 1 was followed, but in this case different aluminum alkyls (AlMe3 AlEt3 and AliBu3) were employed. Table 2 below outlines the performance of these catalyst systems.

[0102]

TABLE 2AlR3Fe†Cat.mmol / gμmol / gAl / FeCat ActFe ActB.D#AlR3SiO2SiO2mol / molg / gCat-hg / gFe-hg / cc1R = Me1.076.313.12,5906.1E050.282R = Et1.076.313.12,8106.6E050.293R = iBu1.076.313.15,9101.4E060.32

[0103]The results of Table 2 illustrate that the catalytic activity will vary depending on the particular components used. In the above instances, the activity and the bulk density increased with use of higher alkyl substituted aluminum compounds.

example 3

[0104]The catalyst compositions and polymerization conditions were the same as those of Example 1 except that different silicas were used in this example. The silicas used for the following examples were based on Grace Davison SP9-263 silica (10 or 20 μ, 500 m2 / g, 1.5 cc / g, 8.6 or 2.9% TV @1750° F.). The results are given in Table 3 below.

[0105]

TABLE 3CatSizeTVAliBu3FeAl / FeCat ActFe ActBD#μ%mmol / gμmol / gmol / molg / gCat-hg / gFe-hg / cc1108.6176.313.13,4608.1E050.362108.6157.317.51,6705.2E050.313202.91114.58.74,8901.2E060.36*4202.9157.317.52,7008.5E050.335202.90.557.38.72,6508.3E050.34*Polyethylene product Mw = 300,000 Mw / Mn = 10.0

[0106]The results of Table 3 illustrate that the total volatile content (TV) of the silica used did not aid in the activity of the formed catalyst composition. The higher TV silicas used in catalyst 1 and 2 actually provided catalyst compositions with lower activity when compared to the back-to-back example (see Catalyst 2 and 4 of Table 3).

[0107]Further, Catalyst...

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Abstract

A catalyst composition, and olefin polymerization process using same, formed from a mixture of a non-aluminoxane aluminum compound, an inorganic oxide and a transition metal bidentate or tridentate complex in certain prescribed proportions. The composition can be formed in a single step or in-situ in the polymerization reaction zone. The resultant catalyst has high activity and is capable of producing high molecular weight olefin products without reactor fouling.

Description

[0001]This is a continuation of U.S. patent application Ser. No. 09 / 431,803, filed Nov. 1, 1999, now abandoned.FIELD OF THE INVENTION[0002]The present invention relates to catalyst compositions suitable for olefinic polymerization, to methods of forming said catalyst compositions and to processes of forming polyolefinic products using the subject catalyst compositions. More particularly, the present invention is directed to a catalyst composition composed of a mixture of a non-alumoxane aluminum compound, an inorganic oxide and a bidentate or tridentate ligand / transition metal complex. The composition is formed by substantially simultaneously mixing the aluminum compound with an inorganic oxide and with the bidentate and / or tridentate ligand / transition metal complex in certain prescribed proportions, as fully described herein below. The subject catalyst compositions have unexpectedly been found to have high catalytic activity and, in the polymerization of olefinic compounds, can pro...

Claims

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Application Information

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IPC IPC(8): B01J31/26C08F4/602C08F4/02C08F4/60C08F10/00C08F10/02
CPCC08F10/00C08F10/02C08F4/7042C08F4/704C08F4/602
Inventor SHIH, KENG YU
Owner SHIH KENG YU